Abstract. Volatile organic compounds (VOCs) emitted by forests strongly affect the chemical composition of the atmosphere. While the emission of isoprenoids has been largely characterized, forests also exchange many oxygenated VOCs (oVOCs), including methanol, acetone, methyl ethyl ketone (MEK), and acetaldehyde, which are less well understood. We monitored total branch-level exchange of VOCs of a strong isoprene emitter (Quercus rubra L.) in a mixed forest in New England, where canopy-level fluxes of VOCs had been previously measured. We report daily exchange of several oVOCs and investigated unknown sources and sinks, finding several novel insights. In particular, we found that emission of MEK is linked to uptake of methyl vinyl ketone (MVK), a product of isoprene oxidation. The link was confirmed by corollary experiments proving in vivo detoxification of MVK, which is harmful to plants. Comparison of MEK, MVK, and isoprene fluxes provided an indirect indication of within-plant isoprene oxidation. Furthermore, besides confirming bidirectional exchange of acetaldehyde, we also report for the first time direct evidence of benzaldehyde bidirectional exchange in forest plants. Net emission or deposition of benzaldehyde was found in different periods of measurements, indicating an unknown foliar sink that may influence atmospheric concentrations. Other VOCs, including methanol, acetone, and monoterpenes, showed clear daily emission trends but no deposition. Measured VOC emission and deposition rates were generally consistent with their ecosystem-scale flux measurements at a nearby site.

The role of volatile organic compounds (VOCs) in plant interactions with the atmosphere is investigated through field observations of branch-level VOC exchange in a New England forest. The data reveal previously unknown sources and sinks of oxygenated VOCs. The emission of methyl ethyl ketone is linked to uptake of methyl vinyl ketone, suggesting the possibility of within-leaf isoprene oxidation. Bidirectional fluxes of some VOCs are also reported, including for benzaldehyde for the first time.

The role of volatile organic compounds (VOCs) in plant interactions with the atmosphere is...